Useful product derived from grapefruit pulp

ABSTRACT

Grapefruit pulp is reacted with an alcohol or ketone, preferably a polyhydric alcohol such as propylene glycol or glycerin, in the presence of a free radical initiator such as ultraviolet light to produce a stable reaction product useful as an ingredient in various cosmetic products and for other purposes. The product is also highly effective as an air deodorizer and an antibacterial and antifungal agent.

United States Patent [1 1 Harich et al.

l l USEFUL PRODUCT DERIVED FROM GRAPEFRUIT PULP [63] Continuation-impart of Ser. No. 27,080, April 9,

1970, abandoned.

[52] U.S. Cl. 204/158 R; 424/195 [51] Int. Cl..... A6lk 27/02; A6lk 27/14; BOlj l/lO [58] Field of Search 424/195; 204/158 R [56] References Cited UNITED STATES PATENTS 5/1941 Ramage 204/158 lO/l944 Windaus 204/158 OTHER PUBLICATIONS U.S. Dispensatory 25th edition (1955) pp. 612, 1038, 1039 & 1135.

[ June 17, 1975 Merck Index Seventh Edition, 1960, pp. 675 & 676.

Chem. Abst. Seventh Collective Index Vol. 56-65, 1962-1966, pg. 104978.

Primary Examiner-Sam Rosen Attorney, Agent, or FirmFinnegan, Henderson, Farabow & Garrett 5 7] ABSTRACT Grapefruit pulp is reacted with an alcohol or ketone, preferably a polyhydric alcohol such as propylene glycol or glycerin, in the presence of a free radical initiator such as ultraviolet light to produce a stable reaction product useful as an ingredient in various cosmetic products and for other purposes. The product is also highly effective as an air deodorizer and an antibacterial and antifungal agent.

10 Claims, 2 Drawing Figures PATENTEDJUN 17 m5 3, 8 90.212

INVENTORS JAKOB HARICH FRANZ F? HARICH 31% an, ZQ/Z demo/2 QYaZmKow ATTORNEYS USEFUL PRODUCT DERIVED FROM GRAPEFRUIT PULP This application is a continuation-in-part of US. application Ser. No. 27.080, filed Apr. 9. 1970, now

abandoned.

This invention relates to the preparation and use of new compounds from citrus products. More particularly, it relates to novel compounds prepared from grapefruit pulp, to the processes for preparing these compounds, and to compositions and methods for their effective use. I

The citrus industry is an important segment ofthe economy of Florida, California, and other parts of the United States. This industry has heretofore largely centered on the production of citrus food products such as orange juice, grapefruit juice and the like.

Large quantities of certain portions of citrus products such as rind, pulp and the like are presently considered to be waste and are merely destroyed or thrown away by commercial fruit or juice processing operations. For

a number of years, however, citrus products have been viewed as a vast, largely untapped reservoir of new chemical materials which could be useful in fields widely divergent from the food industry.

At the same time, citrus products, because of their association with the outdoors, favorable weather conditions, and what may be generally termed a fresh-air,

sprays, deodorants and polishes, lemon and lime shave creams, and many other similar products. Deodorant products of this type'have heretofore merely masked the air with a pleasant citrus-typeodor, without eliminating the basic cause of the odor.

It is a primary object of the present invention to provide new compositions and products of citrus origin, and more particularly from the pulp of grapefruit.

It is a further object of one embodiment of this invention to provide a novel air purifier and sanitizing composition derived from grapefruit pulp.

An object of another embodiment of the invention is to provide a new skin conditioning and cosmetic additive composition.

Still another object of this invention is to provide processes for the production of the new compositions and products of this invention.

Additional objects and advantages of the invention willbe set forth in part in the descriptiont'hat follows and in part will be obvious from that descriptionor may be learned by practice of the invention, the objects being realized and attained by means of the compositions, methods,processes, steps and procedures partic.

ularly pointed out inthe appended claims.

In accordancewith this invention, a. process is pro vided for preparing a novel, citrus-based composition 7 which is an excellent air purifier, deodorizer, and antibacterial and antifungal agent. This process comprises.

reacting grapefruit pulp with an alcohol or ketone, preferably a polyhydric alcohol such as propylene glycol or glycerin, to produce a stable reactionproduct which is useful in many applications, particularly in skin treatment and conditioning and as an ingredient of various types of cosmetic preparations. The reaction product is a highly effective airpurifying composition. 1

This reaction product is also anefficient antibacterial and antifungal agent and can be used in hospitals, doctors offices or the like as a sterilizing medium.

vThe invention consists of the novel steps. methods. processes, procedures, compositions, products and improvements shown and described.

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one embodiment of an apparatus which can be used to practice thc proccss of this invention and. together with the description, serve to explain the principles of the invention.

In the drawings:

. FIG. 1 shows a perspective view of an apparatus useful in practicing the process of this invention.

FIG. 2 shows in section the steam jacket used in heating the contents of the reaction vessel of FIG. I.

In accordance with the invention, the starting material of the present process comprises grapefruit pulp. This pulp is located immediately under the hard, outer rind layer of the skin of fresh grapefruit and is obtained by rnechanically shaving the rind portion from the skin, normally after the inner juice, meat and section skins have been previously removed. The separation of the rind from the inner pulp layer of the skin should be accomplished in such a manner that the inner pulps are not damaged. 1

The pulps used are preferably acquired from fresh, ripe grapefruit obtained when the acid content of the fruit is low, as shown by a pulp pH of about 2.5 to 5.0, and preferably 3.5 to 5.0. The pulp is preferably obtained during the December through April grapefruit season in Florida, and used while it is fresh, for example, after storage at 40 to 45F for a period ofnot over about three (3) days. Longer storage times, up to several months or longer, can be achieved by adding the alcohol or ketone reactant, e.g., propylene glycol or glycerin, to the pulp and storing the two together.

In accordance with the present invention, the grapefruit pulp is reacted with alcohol or ketone, preferably at an elevated temperature and under the influence of ultraviolet radiation, to produce a stable reaction prod- LlCt.

Both monohydric and polyhydric alcohols can be used in this first stage reaction. Thus, suitable alcohols include methanol, ethanol, isopropanol, n-propanol, n-butanol, allyl alcohol, amyl alcohol, tert-amyl alcohol, octyl alcohol, benzyl alcohol, ehtylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, glycerin and the like. Acetone is the presently preferred ketone reactanti The polyhydric, aliphatic alcohols such as propylene glycol and glycerin are greatly preferred reactants in thepresent process, and, in fact, appear. to yield significantly and even unexpectedly superior results over the other alcohol or ketone reactants which can also be used.

The reaction is carried out at room temperature or above, with the reaction proceeding more rapidly at somewhat, elevated temperatures. Reaction temperatures of to 140F are generally used, and temperatures of l l0 to F are preferred.

The ratio of alcohol or ketone to grapefruit pulp used in the reaction can be varied widely. Most of the alcohol used in the preferred procedure described below does not enter into a reaction with the pulp and is believed to serve only a mechanical or extractive function, if any. It is to be understood that the term reaction as used here is intended to have its broadest meaning and includes extractive reactions or any other chemical mechanism that may occur as a result of the practice of the first step of the present process. An excess of alcohol (i.e., propylene glycol) reactant is presently preferred and the reaction is generally carried out using a weight ratio of grapefruit pulp to propylene glycol or glycerin of about l:2. This ratio of reactants has been generally found to yield a superior quality and quantity of intermediate reaction product. Depending on many factors such as frosts, application of pesticide to the fruit, etc.. it may be desirable in some cases to vary the ratio of pulp to alcohol as low as 1:4.5 or even lower.

The reaction of the present invention is preferably carried out in the presence of free radical initiator, most preferably ultraviolet (UV) light. Other conventional radical initiators, such as the chemical initiators tertiary butyl hydroperoxide. azobisbutyronitrile. dicumyl peroxide or the like can also be used. UV light has been found to function well in the present process and is presently preferred. The UV light may be supplied by commercially available UV light sources or even by sunlight.

A suitable system for carrying out this reaction is illustrated in the attached drawing. Referring to the drawing, one (1) part by weight of grapefruit pulp is placed in a stainless steel reaction vessel indicated generally as 10, and two parts by weight of alcohol or ketone, preferably propylene glycol or glycerin. are added over the pulp and circulated through tank and reaction tube 12 by means of pump 14. The reaction mixture in tank 10 is circulated through clear reaction tube 12, which is appropriately made of glass or clear plastic. such as polypropylene, Teflon. or Pyrex. for a period of about 6 to 24 hours preferably at a temperature of about i 10 to 120F. The mixture is subjected to ultraviolet radiation from UV source 16 during its passage through tube 12. This light can be supplied for example from a General Electric Black UV light source with Integral Filter No. F 2OTl2-BL-20 watts. 24 inches long.

The mixture is, of course, continuously recirculated through the grapefruit pulp in reaction vessel 10.Referring again to the drawing, reaction vessel 10 can, for example, comprise a stainless steel, steamjacketed 252 gal. reaction vessel equipped with a 1.6 horsepower, 3,400 rpm stainless steel pump 14. 1 /2 to 2-inch clear, plastic tubing 12 is provided for recirculation of the reaction mixture through a source of ultraviolet light 16. The light source can comprise four (24 inch) ultraviolet tubes of the type described above, with two tubes on each side of the plastic tubing and a 3 /2 -inch center space between the sets of UV tubes.

The reaction mixture is preferably introduced back into tank 10 from tubing 12 through a sprinkle outlet 18. Two-way gate valves and 21 allow the reaction mixture to be either recirculated by pump 14 or drained by gravity to remove it from the reaction vessel. This draining and recirculating preferably take place through a screen drain 22 located at the bottom of the reaction vessel. This drain can comprise, for example, a 16 mesh screen. Stirrer 24, driven by motor 26 can be used to achieve agitation if desired, although agitation is not required.

The propylene glycol, glycerin or other alcohol or kctone component used in the reaction is preferably U.S.P. grade. The reaction vessel is preferably operated at a pressure of about 5 to 20 p.s.i.g.

The reaction product produced in the first-stage reaction contains substantial amounts of unreacted propylene glycol or other alcohol or ketone and water. and a relatively minor amount of one or more active components which have not been totally identified. For example. at 1:2 ratios of pulp to propylene glycol. the reaction product is believed to contain about to percent unreacted propylene glycol, about 10 percent water and about 0.5 to 4 percent of active component or components. This reaction product is storage stable and is useful in the cosmetic and veterinary fields, particularly for application to the skin, for example, in treatment or conditioning of the epidermis, stratum corneum and sebaceous gland areas of human and animal tissue. It is believed that the active components of this product play an important role in conditioning cells, tissue, and fibrous membrane in the circulation system of the open skin surface.

This product has effective antibacterial and antifungal properties, particularly in purified form, and these may contribute to its beneficial effect in cosmetic preparations. I

The reaction product of this invention thus is a highly beneficial, natural skin conditioner, which particularly improves the texture and softness of the horny layer and lipoidal portion of the skin of both humans and animals. The material may thus be incorporated in minor amounts of about 1 to 2 percent in conventional cosmetic bases such as cleansing cream, ointment or surfactants of the Tween-80 variety and applied as it cosmetic or softening agent to the skin.

This product can be beneficially incorporated in a wide variety of cosmetic products, for example, in suntan lotion, suntanning lotion, night cream. cleansing cream, moisture foundation cream, cream hair rinse, skin freshener, hand and body lotion, and anti-dandruff shampoos, among others. Suitable formulations for many of such products using the reaction product of the invention are illustrated in the specific examples set forth hereinafter, wherein the reaction product is referred to as CA-9O Base. It is to be understood, however, that these particular formulations are only exemplary and that the compositions of this invention can be used in small amounts effective for skin conditioning, for example, on the order of about 0,5 to 2 percent by weight, in virtually any cosmetic base material for shampoos and other cosmetic formulations that contact the skin.

The term final reaction product" is used herein to refer to this product without limiting its production to any particular chemical mechanisms that may occur at any stage of the process so long as the designated process steps are followed.

This reaction product also is a highly efficient room air deodorizer. Prior art citrus-type deodorizers are generally merely citrus-type perfumes which mask the air with a citrus odor, thereby overpowering other malodorous components in the air.

On the other hand, it is believed that the reaction product of this invention achieves its deodorizing effect, at least in part, by removal of the root causes of bad odors. Thus, in many instances bad, musty odors are caused by bacterial or fungal action. It has been found that the reaction product of the present invention is a highly effective bactericidal agent. and it is believed that this antibacterial action contributes significantly to the deodorizing action of the composition. This deodorizing action is illustrated more specifically in the specific examples that follow.

Use of the reaction product of this invention as an air deodorizer is particularly effective in closed air systems, such as internal bathrooms or powder rooms in houses, apartments, motels. hospitals. and the like. It has been found that circulation of stale, musty or odoriferous air into contact with this product can eliminate completely the need for exhaust fan systems and attendant duct work in such structures. Deodorizer systems using the final reaction product of this invention can also be used in submarines, automobiles, trains, and in any other place where stale, musty, or offensively odoriferous air is present.

The deodorizer of this invention can be provided in solid form as well as liquid. The solid form is provided by admixing the reaction product of this invention with an inert, nonodorous solid, such as, for example, lauryl alcohol, synthetic wax, or natural beeswax. Normally, use of the reaction product in liquid form is preferred due to the superior deodorization achieved.

The deodorizer can be used in aerosol form with the reaction product being dispersed in an inert propellant. such as Freon or the like, under conventional aerosol spray pressures of, for example, about 35 to 40 p.s.i.g. The deodorizing product of this invention also can be used in highly effective treatment of sewage to eliminate the obnoxious odors often emitted from lift stations or primary or secondary sewage treatment facilities. The product is periodically sprayed or injected into or onto the sewage being treated.

Because of its bactericidal and fungicidal properties, the reaction product of this invention can also be used as a sanitizing or sterilizing agent in hospitals, doctors offices, or the like. It is particularly effective for such uses because of its efficient action against staphylococcus aureus and pseudomonas aeruginosa.

The following specific examples are presented to afford a better understanding of the present invention to those skilled in the art. It is to be understood that these examples are intended to be illustrative only and are not intended to limit the invention in any way.

EXAMPLE 1 One pound (454 gms.) of fresh grapefruit pulp prepared by mechanically removing the outer rind from the inner pulp of grapefruit picked 2 days previously is placed into a laboratory stainless steel reactor and 2 pounds (908 gms.) of propylene glycol U.S.P. is added over the grapefruit pulp. The liquid portion of the reac tion mixture is circulated through the grapefruit pulp and through Teflon tubing surrounded by an ultraviolet light source, in a system of the type illustrated in the at tached drawings, for a period of 24 hours. The system is maintained at a temperature of 1 to 120F during this period. Heating is accomplished by introducing steam at l020 p.s.i.g. into steam jacket 34 (FIG. 2) through steam inlet 30. Outlet 32 allows removal of spent steam. The ultraviolet light source consists of four ultraviolet tubes, with two tubes located on each side of the clear, Teflon recycle tube.

A total of 872 gms. of liquid reaction product is then separated from the grapefruit pulp residue by straining through a 16 mesh screen. This reaction product is storage stable for an indefinite period of time.

EXAMPLE 2 The procedure of Example 1 is repeated in this example except that 2 parts by weight of glycerin are substituted for propylene glycol in the reaction step. The results achieved are substantially the same as those achieved in Example 1.

EXAMPLE 3 The process of Example l is repeated in this example, except that commercial size equipment is utilized. A stainless steel tank having a capacity of 252 gals, and a 1 /2 in. diameter polypropylene tubing is used to cycle the reaction mixture through the pulp and ultraviolet light source. That UV source comprises four 24 in. ultraviolet tubes, with two tubes set on each side of the tubing. The space between the opposing sets of tubes is 3% in.

One hundred lbs. of fresh grapefruit pulp which has been stored for 1 day at 40 to 45F is added to the reactor and 200 lbs. of propylene glycol U.S.P. is added through a monitoring pump. The reaction is carried out at 1 10 to F with constant cycling for a period of 12 hours and 195 lbs. of liquid reaction product is then separated by draining from the reaction vessel through a 16 mesh filtration screen. A portion of this reaction product is stored and again found to be storage stable for an indefinite period of time.

The sample is found to have substantially the same properties as that produced in the laboratory scale process of Example 1.

EXAMPLE 4 The procedure of Example 3 is repeated in this example except that during the initial reaction between the grapefruit pulp and the propylene glycol, a cloudy, unstable reaction product is produced. it is believed that this instability is probably due to hard frost encountered by the fruit during its growth. The reaction is stopped after about 6 hrs. and additional propylene glycol is added to reduce the ratio of pulp to propylene glycol to about 1:45. The reaction is then continued for 12 hours under the conditions described in Example 3 and the remainder of the procedure of that example is carried out. A product substantially similar to that of Example 3 is produced.

EXAMPLE 5 In this example various alcohols, ketones and other solvents are substituted for the propylene glycol or glycerin reactant used in the reaction of Examples l-4 above. The procedure of Example 1 is generally followed, using 50 grams of grapefruit pulp and 100 grams of alcohol, ketone or other reactant. The reaction is carried out under UV light at temperatures ranging from 90 to F, for reaction times between 12 and 24 hours.

The reaction products of these reactions are filtered, diluted 50/50 with methanol, heated slightly to 90-l 10F and then allowed to set for about 10 minutes. Eight (8) ml. samples are then centrifuged and the upper liquid phase decanted to leave a small accumulation of a brown gel-type material in the bottom of the tubes used in centrifuging. The total amount of this gel produced in each of the reactions is accumulated and weighed. The gel is washed with acetone and all liquid removed by vacuum. The amounts and nature of the products produced in reactions of grapefruit pulp with various alcohols, ketones and other typical solvent rcactants are shown in Table ll below. As is apparent from the data of Table ll, liquid, alkyl polyhydric alco hols. and lower alkyl ethers thereof. are particularly effective reactants.

When this gel product is placed under refrigeration at 25 to 30F for about 72 hours, the formation of white crystals is observed. These crystals are washed with cold water and filtered. They are soluble in hot water and insoluble in ether and chloroform. The

on the surface of test plates covered with freshly prepared Nutrient Agar media. Test filters previously dipped in the compositions of the invention and control filters dipped in propylene glycol are placed in the center of the plates and the plates are incubated for 48 hours at 375C. The effectiveness of the compositions against the bacteria is evaluated by measurement of the inhibition zone as in the previous examples. The results are reported in Table III.

TABLE ll Amount of Product Description Reactant (mg) of Product methanol 7 lemon yellow ethanol, 95% 6 lemon yellow n-propanol 20 lemon yellow isopropanol. anhydrous 9971 50 lemon yellow n-butanol l8 lemon yellow l-decanol hazy Z-ethyl hcxanol O hazy allyl alcohol lemon yellow amyl alcohol 4 lemon yellow t-amyl alcohol 7 lemon yellow octyl alcohol 2 lemon yellow benzyl alcohol 4 lemon yellow propylene glycol, U.S.P. 72 clear lemon yellow glycerin (synthetic 99.571) 59 clear lemon yellow glycerin (U.S.P. 99.571) 64 clear lemon yellow glycerin (U.S.P. 96%) 65 clear lemon yellow triethylene glycol 46 clear lemon yellow tetraethylene glycol 6l clear lemon yellow dipropylene glycol 63 clear lemon yellow tripropylene glycol 51 clear lemon yellow ethylene glycol n'butyl ether 48 clear lemon yellow ethylene glycol ethyl ether 49 clear lemon yellow diethylene glycol n-butyl ether 52 clear lemon yellow diethylene glycol methyl ether 47 clear lemon yellow polyethylene glycol 31 clear lemon color acetone 2] light yellow methyl ethyl ketone 2 lemon yellow benzene 3 light yellow xylene l hazy yellow ether 0 light clear yellow cyclohexane l hazy yellow chloroform 0 light clear yellow methyl chloroform 0 light clear yellow methylene chloride 0 light yellow tetrachloroethylene 0 light yellow TABLE III Zone of Composition Dilution Inhibition Crystals from propylene glycol l to I00 ltl nini Liquid reaction product from propylene glycol l to llll) 2 mm Liquid reaction product from propylene glycol full strength 4 5 nnn Crystals from acetone 1 to lot) 5 mm Liquid reaction product from acetone 1 to I00 no overgrowth Liquid reaction product from acetone full strength I mm Crystals from I to 5.5 mm

. isopropanol Liquid reaction product from isopropanol l to 100 no overgrowth Liquid reaction product I from isopropanol l to 100 1.5 mm

Propylene glycol l to 100 no overgrowth (Control) Propylene glycol full strength 2.5 mm

EXAMPLE 6 Ten (10) white albino rabbits, days old and having body weights of 1310 to 1350 gms. are examined for normalcy and skin condition. The animals are then isolated in separate holding cages and allowed food and -water ad libitum. After 7 days of observation, the bellies of the rabbits are clipped free from hair and their skin examined to determine that it is normal. The reaction product produced in Example 1 (CA-90 Base) is applied to five animals in a 5 percent solution in Tween-80 and to five other animals in a 2 percent solution in a commercial cleansing cream. The skin area is thoroughly dried with a hair dryer before application. After dosing, the animals are wrapped in a plastic film to prevent evaporation. After 24 hrs. exposure, the covering bandage and plastic wrap are removed and the exposed skin areas examined, washed with lukewarm water and soap, rinsed and dried, and then reexamined for irritation, edema or erythema. The animals skins are found to be uniformly soft and smooth with no irritation or sensitization. It is concluded that cosmetic creams containing the first reaction products of this invention would be of great value as skin condition ers.

The first reaction product of Examples 3 and 4 is incorporated into corn oil and commercially available cosmetic bases, and is applied in both of these forms and in undiluted form to the hands of human volunte'ers. It is found to leave the hands in uniformly smooth and soft condition, again indicating the utility of the intermediate composition of this invention as a cosmetic skin conditioning agent.

EXAMPLE 7 Component A Cetyl alcohol The ingredients of Components A and B are separately mixed, melted, and heated to a temperature of 170E. The components are then mixed by adding A to B using a high speed mixer The mixing is continued with co'0ling to 130F, andComponent C is then added. Mixing and cooling continue to room temperature, and the product is then allowed to stand overnight r emixed and bottled.

EXAMPLE 8 A cream hair rinse composition is prepared having the following formulation, in parts by weight:

Component A Triton X400 8.0 Cerasynt 660 (Dow Corning) 2.5 Sodium chloride 0.5 CA-90 Base (Example 4) 1.5 7.5

Water (deionized) 8 Component 8 Citric acid q.s. to pH 3.0-3.5

Component C Perfume (H36 Van Dyk Color The ingredients of Component A are heated at 70 to- 75C until homogeneous, and then removed from the heat and cooled to 40-45C. Component B is added with agitation. Component C is then added and the agitation is continued until all ingredients are thoroughly dispersed. The product is then filled into containers.

EXAMPLE 9 A night cream product is prepared in this example, having the following formulation, in parts by weight:

Component A Lanolin (anhydrous) U.S.P. Cetyl alcohol Stcaric acid (triple-pressed) lsopropyl myristate Mineral oil (light) U.S.P. 2210 lgepal CO 630 (General Aniline) l.5 Propyl paraben U.S.P. 0.125 Allantoin 0.5

Component B Methyl paraben U.S.P. 0.0675 Water 47.2975

g m (R.T. Vanderbilt) -Continued Component A Component C Carhoxymethyl cellulose (7-HP) 0.25

Component D Sorl itol solution U.S.P. 5.0

l'riethaliolamine 2.75

Component F.

(A- Base (Example 4) 0.5

The ingredients of Component A are melted and heated to 160F. Component B is prepared by heating the water to l70F and adding the methylparaben. using a high speed mixer, followed by Veegum. As soon as Component B is homogenous, Component C is added to it and mixed until smooth. Component A is added to Components B-C with mixing, and Component D is then added. The resulting mixture is cooled to F and the CA-90 Base (Component E) is added with mixing. The product is cooled to room temperature, allowed to sit for 24 hours and filled into containers. Tests show it to be an excellent skin conditioner.

EXAMPLE l0 A moisture foundation cream is prepared having the following formulation, in parts by weight:

Component A Lanolin (anhydrous) U.S.P. 0.75 lsopropyl myrislate 2.00 Stearie acid (triple-pressed) l4.00 Cetyl alcohol 1.00 Propyl parahen U.S.P. 0.0625

Component B Methyl parahen U.S.P. 0.125 Water (soft) 59.] I25 Veegum (R T. Vanderbilt) 0.5 Allantoin 0.5

Component C Potassium hydroxide (36Be) 0.5 Triethanolamine 0.375 Sorbitol solution U.S.P. 4.0 Glycerin U.S.P. l6.00

CA-90 Base (Example 4) 0.5 Perfume 0.375

Component A is melted and brought to a temperature of 170F. The ingredients of Component B are mixed with a high speed mixer until dissolved and heated to 170F. The ingredients of Component C are heated to 170F and mixed with Component B. Component A is mixed with Components B and C with a high speed mixer and the resulting mixture is cooled to F and Component D is added. The product is cooled to room temperature, allowed to stand overnight, remixed and filled.

Use of this formulation is shown to produce improved skin conditioning.

EXAMPLE 1 1 i A skin freshener composition is prepared by mixing the following ingredients, in parts by weight:

Ethyl alcohol (39C) 17.10 Carhitol 6.40 CA-90 Base (Example 4) 2.00 Benzoic acid 0.19

'Continued Perfume (Orange Fluerr M-l l '9) Distilled water EXAMPLE l2 A hand and body lotion composition prepared having the following formulation. in parts by weight:

Component A Mineral oil (li ht) 2.50 Standamul l4 4-E (Atlas Chemical) 2.50 Stearic Acid (triple-pressed) 2.60 'l'egin (Churchill Co.) L50 Acetulan (Churchill Co.) L Allantoin 0.20 Lantrol (Dow Chemical) 0.50 Propyl p-hydroxybenzoate 0.10

Component B CA JO Base (Example 4) L00 Triethanolamine (95 9971 0.70 Methyl p-hydroxybenzoate 0.l0 Propylene glycol U.S.P. 1.00 Water 86.25

Components A and B are separately heated to 175F and Component 8 is then slowly added to Component A with constant agitation. Perfume and color are added as desired at 100F and the product is then cooled and filled.

EXAMPLE l3 A cleansing cream composition is prepared having the following formulation in parts by weight:

Component A Lanolin (anhydrous) U.S.P. Cetyl alcohol Olcic acid isopropyl myristate Mineral oil (Light) U.S.P.

lgepal CO 630 Propyl parabcn Allantoin Component B Methyl paraben Water Veegum (R.T. Vanderbilt) Component C Carboxymethyl cellulose (7-HP) Component D Glycerin U.S.P. Triethanolamine Component E CA-90 Base (Example 4) 0.5 The ingredients of Component A are melted and brought to a temperature of 170F. The water of Component B is heated to 160F and the methyl paraben and then the Veegum are added. Component D is added to the B-C mixture, followed by addition of Component A. Mixing is continued with cooling to 120F and Component E is then added. The product is allowed to stand 24 hours and filled. This formulation is tested and found to produce improved skin conditioning. I

EXAMPLE 14 A protein anti-dandruff shampoo composition is prepared by admixing the following ingredients in the amounts shown in parts by weight:

Potassium salt of untlecylenyl- 20.00

polypeptide condensate Potassium salt of cocoylpolypeptide condensate Sodium salt of collagen protein hydrolysate Sodium lauryl ether sulfate 4 (A- Base (Example 4) Herbal extracts as a perfume EXAMPLE l5 Asuntan lotion composition is prepared having the following formulation, in parts by weight:

(ilyceryl para-aminobenzoate l.5 Mineral oil (light) 4.0 isopropyl myristate 4.0 isopropyl alcohol (anhyd) 28.5 Dipropylene glycol 28.0 CA-90 Base (Example 4) L5 Gentron-l l (Freon) 32.5

Perfume the final suntan lotion product.

The present invention in its broader aspects is not limited to the specific details shown and described above, but departures may be made from such details without departing from the principles of the invention and without sacrificing its chief advantages.

What is claimed is:

1. A process for preparing an organic composition which comprises contacting the pulps of grapefruit with a nontoxic liquid, alkyl polyhydric alcohol or a lower alkyl ether thereof in the presence of ultraviolet light to form a reaction product, and separating this product from the pulp residue.

2. The process of claim 1 wherein the grapefruit pulp is contacted with an alcohol, selected from the group consisting of propylene glycol, glycerin, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycol, ethylene glycol n-butyl ether, ethylene glycol ethyl ether, diethylene glycol n-butyl ether, and diethylene glycol methyl ether.

3. The process of claim 2 wherein the pulp reactant comprises the inner pulp of fresh grapefruit having a lowacid content as shown by a pH of about 2.5 to 5.

4. The process of claim 2 wherein the grapefruit pulp is contacted with propylene glycol or glycerin at a weight ratio of about 1:2, and the reaction is carried out at an elevated temperature in the presence of ultraviolet light. Y

5. The process of claim 1 wherein the grapefruit pulp is contacted with propylene glycol.

6. The process of claim 1 wherein the grapefruit pulp is contacted with glycerin.

7. A process for forming an organic composition which comprises contacting fresh grapefruit pulp having a low acid content, as shown by a pH of about 2.5 to 5.0, with an excess of propylene glycol or glycerin in ene glycol. triethylene glycol, tetraethylene glycol. tripropylene glycol, polyethylene glycol, ethylene glycol n-butyl ether. ethylene glycol ethyl ether, diethylene glycol n-butyl ether. and diethylene glycol methyl ether.

10. An organic composition comprising the product obtained by contacting fresh grapefruit pulp having a pH of about 2.5 to 5.0 with a non-toxic liquid. alkyl polyhydric alcohol or a lower alkyl ether thereof in the presence of ultraviolet light. 

1. A PROCESS FOR PREPARING AN ORGANIC COMPOSITION WHICH COMPRISES CONTACTING THE PULPS OF GRAPEFRUIT WITH A NONTOXIC LIQUID, ALKYL POLYHYDRIC ALCOHOL OR A LOWER ALKYL ETHER THEREOF IN THE PRESENCE OF ULTRAVIOLET LIGHT TO FORM A REACTION PRODUCT, AND SEPARATING THIS PRODUCT FROM THE PULP RESIDUE.
 2. The process of claim 1 wherein the grapefruit pulp is contacted with an alcohol, selected from the group consisting of propylene glycol, glycerin, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycol, ethylene glycol n-butyl ether, ethylene glycol ethyl ether, diethylene glycol n-butyl ether, and diethylene glycol methyl ether.
 3. The process of claim 2 wherein the pulp reactant comprises the inner pulp of fresh grapefruit having a low acid content as shown by a pH of about 2.5 to
 5. 4. The process of claim 2 wherein the grapefruit pulp is contacted with propylene glycol or glycerin at a weight ratio of about 1:2, and the reaction is carried out at an elevated temperature in the presence of ultraviolet light.
 5. The process of claim 1 wherein the grapefruit pulp is contacted with propylene glycol.
 6. The process of claim 1 wherein the grapefruit pulp is contacted with glycerin.
 7. A process for forming an organic composition which comprises contacting fresh grapefruit pulp having a low acid content, as shown by a pH of about 2.5 to 5.0, with an excess of propylene glycol or glycerin in the presence of ultraviolet light at a temperature of about 90 to 140*F for a period of about 6 to 24 hours to form a reaction product.
 8. An organic composition comprising the product obtained by contacting grapefruit pulp with a non-toxic liquid, alkyl polyhydric alcohol or a lower alkyl ether thereof in the presence of ultraviolet light, to form a reaction product, and separating this product from the pulp residue.
 9. The composition of claim 8 wherein the alcohol is selected from the group consisting of propylene glycol, glycerin, ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycol, ethylene glycol n-butyl ether, ethylene glycol ethyl ether, diethylene glycol n-butyl ether, and diethylene glycol methyl ether.
 10. An organic composition comprising the product obtained by contacting fresh grapefruit pulp having a pH of about 2.5 to 5.0 with a non-toxic liquid, alkyl polyhydric alcohol or a lower alkyl ether thereof in the presence of ultraviolet light. 